Mineral-Enhanced Polyacrylic Acid Hydrogel as an Oyster-Inspired Organic-Inorganic Hybrid Adhesive.

Underwater adhesion is crucial to many marine life forms living a sedentary lifestyle. Amongst them, mussel adhesion has been mostly studied, which inspires numerous investigations of 3,4-dihydroxyphenylalanine (DOPA)-based organic adhesives. In contrast, reef-building oysters represent another important "inorganic" strategy of marine molluscs for adhesion by generating biomineralized organic-inorganic adhesives, which is still rarely studied and no synthetic analogues have ever been reported so far. Here, a novel type of oyster-inspired organic-inorganic adhesive based on a biomineralized polyelectrolyte hydrogel is reported, which consists of polyacrylic acid physically cross-linked by very small amorphous calcium carbonate nanoparticles (<3 nm). The mineral-enhanced polyelectrolyte hydrogel adhesive is shown to be injectable, reusable, and optically clear upon curing in air. Moreover, comparable adhesion performance to DOPA-based adhesives is found for the hydrogel adhesive in both dry and wet conditions, which can even be further enhanced by introducing a small amount of second large cross-linker such as negatively charged nanoparticles. The present mineral hydrogel represents a new type of bio-inspired organic-inorganic adhesive that may find a variety of potential applications in adhesive chemistry.

Controlled nanoparticle formation by diffusion limited coalescence.

Polymeric nanoparticles (NPs) have great application potential in science and technology. Their functionality strongly depends on their size. We present a theory for the size of NPs formed by precipitation of polymers into a bad solvent in the presence of a stabilizing surfactant. The analytical theory is based upon diffusion-limited coalescence kinetics of the polymers. Two relevant time scales, a mixing and a coalescence time, are identified and their ratio is shown to determine the final NP diameter. The size is found to scale in a universal manner and is predominantly sensitive to the mixing time and the polymer concentration if the surfactant concentration is sufficiently high. The model predictions are in good agreement with experimental data. Hence the theory provides a solid framework for tailoring NPs with a priori determined size.

Polymer compatibility in two dimensions. Modeling of phase behavior of mixed polymethacrylate Langmuir films.

We analyze the possibility of polymer blends undergoing phase separation in two dimensions. To this end, we investigate a model system consisting of water-supported Langmuir monolayers, obtained from binary polyalkyl-methacrylate mixtures (PXMA, where X stands for any of the type of ester side groups used: M, methyl-; E, ethyl-; B, butyl-; H, hexyl-; O, octyl-; L, lauryl-methacrylate), by means of self consistent field (SCF) calculations. In particular, we address the conditions which determine demixing and phase separation in the two-dimensional system, showing that a sufficient chain length mismatch in the ester side group moieties is able to drive the polymer demixing. When the difference in length of the alkyl chain of the ester moieties on the two types of polymers is progressively reduced, from 11 carbon atoms (PMMA/PLMA) to 4 carbons only (POMA/PLMA), the demixing tendency is also reduced. The polymer/subphase interactions affect more the distribution of the polymer coils in the POMA/PLMA blend monolayer. Mixing of the two polymers is observed, but also a partial layering along the vertical direction. We also add, to a PMMA/PLMA blended monolayer, a third component, namely, a symmetrical diblock copolymer of the type PLMA-b-PMMA. We observe adsorption of the diblock copolymer exclusively at the contact line between the two homopolymer domains, and a concomitant lowering of the line tension. The line tension varies with the chemical potential of the diblock copolymer according to Gibbs' law, which demonstrates that PLMA-b-PMMA can act as a "lineactant" (the equivalent of a surfactant in two-dimensional systems) in the binary demixed PMMA/PLMA Langmuir monolayer.

PMMA highlights the layering transition of PDMS in Langmuir films.

We report a system consisting of a mixed Langmuir monolayer, made of water-insoluble, spreadable, fluid-like polymers polydimethylsiloxane (PDMS) and polymethylmethacrylate (PMMA) with a minority P(DMS-b-MMA) copolymer. We have performed both Langmuir trough pressure/area isotherm measurements and Brewster angle microscopy (BAM) observations and complement the experiments with molecularly detailed self-consistent field (SCF) calculations. PDMS undergoes a layering transition that is difficult to detect by BAM. Addition of PMMA gives contrast in BAM, now showing a two-phase system: if this would consist of separate two-dimensional (2D) PMMA and PDMS phases, a PDMS-PMMA diblock should accumulate at the phase boundary. However, the diblock copolymer of PDMS-PMMA failed to show the expected "lineactant" behavior, i.e., failed to accumulate at the phase boundary. The calculations point to a nontrivial arrangement of the polymer chains at the interface: in mixtures of the two homopolymers, in a rather wide composition ratio, we find a vertical (with respect to the air/water interfacial plane) configuration, with PMMA sitting preferably at the PDMS/water interface of the thicker PDMS film, during the PDMS layering phase transition. This also explains why the diblock copolymer is not a lineactant. Both PMMA and P(DMS-b-MMA) are depleted from the thin-thick PDMS film interface, and the line tension between the phases is, consequently, increased, in the binary mixtures as well as in the ternary ones.

Polymers at the water/air interface, surface pressure isotherms, and molecularly detailed modeling.

Surface pressure isotherms at the air/water interface are reproduced for four different polymers, poly-L-lactic acid (PLLA), poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and poly(isobutylene) (PiB). The polymers have the common property that they do not dissolve in water. The four isotherms differ strongly. To unravel the underlying details that are causing these differences, we have performed molecularly detailed self-consistent field (SCF) modeling. We describe the polymers on a united atom level, taking the side groups on the monomer level into account. In line with experiments, we find that PiB spreads in a monolayer which smoothly thickens already at a very low surface pressure. PMMA has an autophobic behavior: a PMMA liquid does not spread on top of the monolayer of PMMA at the air/water interface. A thicker PMMA layer only forms after the collapse of the film at a relatively high pressure. The isotherm of PDMS has regions with extreme compressibility which are linked to a layering transition. PLLA wets the water surface and spreads homogeneously at larger areas per monomer. The classical SCF approach features only short-range nearest-neighbor interactions. For the correct positioning of the layering and for the thickening of the polymer films, we account for a power-law van der Waals contribution in the model. Two-gradient SCF computations are performed to model the interface between two coexistent PDMS films at the layering transition, and an estimation of the length of their interfacial contact is obtained, together with the associated line tension value.

Osmotic shrinkage and reswelling of giant vesicles composed of dioleoylphosphatidylglycerol and cholesterol.

The osmotic shrinkage of giant unilamellar dioleoylphosphatidylglycerol (DOPG) vesicles in a hypertonic osmotic solution is investigated. The volume reduction for given membrane area leads to a vesiculation of the bilayer into the interior of the giant. The size of the daughter vesicles that appear inside the giant is uniform and an increasing function of the cholesterol content, but independent of the osmotic gradient applied. The radius of the daughter vesicles increases from 0.2 microm to 3.0 microm when the cholesterol content is changed from 0 to 40%. It is argued that the size of the daughter vesicles is regulated by the membrane persistence length, which is an exponential function of the mean bending modulus. From the kinetics of shrinkage it follows that approximately 14% of the daughter vesicles remain attached to the mother giant. This is in reasonable agreement with osmotic swelling experiments which show that approximately 11% of the daughter vesicles is available for area expansion.

Persistence length of wormlike micelles composed of ionic surfactants: self-consistent-field predictions.

The persistence length of a wormlike micelle composed of ionic surfactants C(n)E(m)X(k) in an aqueous solvent is predicted by means of the self-consistent-field theory where C(n)E(m) is the conventional nonionic surfactant and X(k) is an additional sequence of k weakly charged (pH-dependent) segments. By considering a toroidal micelle at infinitesimal curvature, we evaluate the bending modulus of the wormlike micelle that corresponds to the total persistence length, consisting of an elastic/intrinsic and an electrostatic contribution. The total persistence length increases with pH and decreases with increasing background salt concentration. We estimate that the electrostatic persistence length l(p,e)(0) scales with respect to the Debye length kappa(-1) as l(p,e)(0) approximately kappa(-p) where p approximately 1.98 for wormlike micelles consisting of C(20)E(10)X(1) surfactants and p approximately 1.54 for wormlike micelles consisting of C(20)E(10)X(2) surfactants. The total persistence length l(p,t)(0) is a weak function of the head group length m but scales with the tail length n as l(p,t)(0) approximately n(x) where x approximately 2-2.6, depending on the corresponding head group length. Interestingly, l(p,t)(0) varies nonmonotonically with the number of charged groups k due to the opposing trends in the electrostatic and elastic bending rigidities upon variation of k.

Opposing effects of cation binding and hydration on the bending rigidity of anionic lipid bilayers.

We correlate the molecularly realistic self-consistent field predictions for the mean bending modulus kc of charged lipid vesicles with experimental observations of the size R of corresponding vesicles that are produced by the freeze-thaw method. We elaborate on the Ansatz that the bending modulus is related to the membrane persistence length and that this length scale sets the radius of the vesicles. Alkali cations have a remarkable effect on the mean bending modulus and thus on the equilibrium radius of negatively charged entropically stabilized dioleoylphosphatidylglycerol (DOPG) vesicles. Where cation hydration typically results in thicker and thus stiffer membranes, specific adsorption to the bilayer surface results in a decrease of the surface charge density and the thickness of the membrane-associated electric double layer. As a result of these opposing effects on kc and R, the largest DOPG vesicles are found in the presence of K+, which combines an intermediate hydration enthalpy and PG-binding affinity.

On the stability of (highly aggregated) polyelectrolyte complexes containing a charged-block-neutral diblock copolymer.

Using light scattering and cryogenic transmission electron microscopy, we show that highly aggregated polyelectrolyte complexes (HAPECs) composed of poly([4-(2-aminoethylthio)butylene] hydrochloride)49-block-poly(ethylene oxide)212 and poly(acrylic acid) (PAA) of varying lengths (140, 160, and 2000 monomeric units) are metastable or unstable if the method of preparation is direct mixing of two solutions containing the oppositely charged components. The stability of the resulting HAPECs decreases with decreasing neutral-block content and with increasing deviation from 1:1 mixing (expressed in number of chargeable groups) of the oppositely charged polyelectrolytes, most probably for electrostatic reasons. The difference between the metastable and stable states, obtained with pH titrations, increases with increasing PAA length and increasing pH mismatch between the two solutions with the oppositely charged components.

Direct measurement of depletion and hydrodynamic forces in solutions of a reversible supramolecular polymer.

In this paper, the investigation of surface forces in semidilute solutions of a nonadsorbing hydrogen-bonded reversible supramolecular polymer is described. Colloidal probe atomic force microscopy was used for direct measurement of depletion forces. Hydrodynamic drag on the AFM cantilever with the colloidal probe was measured both far away from and close to the planar substrate surface. The results indicate that the presence of the depletion layer causes slip at the surfaces with a large apparent slip length. Our analysis explains how the presence of slip enables the measurement of (relatively weak) depletion forces in solutions with a high viscosity by significantly reducing the hydrodynamic forces. The range and magnitude of the measured depletion forces are qualitatively in agreement with previous experiments and theoretical predictions. Due to the relatively large experimental error, no quantitative conclusions can be drawn. Depletion-induced phase separation of suspensions of stearylated silica particles was also observed. Phase separation becomes more pronounced with increasing polymer concentration.

Micellization of telechelic associative polymers: self-consistent field modeling and comparison with scaling concepts.

We present numerical results from self-consistent field calculations on the micellization of telechelic associative polymers and their mono-functional analogues. These results are confronted with relatively simple scaling concepts. The proportionality of the critical micelle concentration (CMC) with the hydrophilic backbone length, as found in the calculations, shows good correspondence with a scaling argument based on the entropic penalty of loop formation. It is also shown that models for the conformation of spherical brushes can be applied to predict the structure of the flowerlike micelles formed by these telechelic polymers. Furthermore, we find good agreement between the numerical dependence of the aggregation number upon both backbone and terminal hydrophobe length and an analytical expression derived from the well-known Daoud-Cotton model by introducing a correction for the finite size of the micellar core.

Wetting in a colloidal liquid-gas system.

We present first observations of wetting phenomena in depletion interaction driven, phase separated colloidal dispersions (coated silica-cyclohexane-polydimethylsiloxane). The contact angle of the colloidal liquid-gas interface at a solid substrate (coated glass) was determined for a series of compositions. Upon approach to the critical point, a transition occurs from partial to complete wetting.